Lubricating composition



Patented June 1,1943

STATES 2,320,984 7 LUBRICATING ooMrosrrroN Carl F. Prutton, EastCleveland, Ohio, assignor, by mesne assignments, to The Lubri-ZolDevelop-' ment Corporation, Cleveland, Ohio, a corporation of DelawareNo Drawing. Application December-'4, 1934, Serial No. 755,987

15 Claims.

the combined use as a lubricating composition of organic oxygen bearingcompounds and or-' ganic halogen bearing compounds and the comtainaddition a'gents for the purpose of improving the lubricating propertiesof such oil base and more particularly to impart extreme pressurecharacteristics to such composition.

As disclosed in my 'co-pending application Serial No. 638,599 filedOctober 19, 1932, certain desirable improvements in the lubricatingproperites of a lubricatingoil maybe secured-by the combinationtherewith of certain halogenated additions, particularly halogenated ormore specifically chlorinated organic compounds.

The present invention relates to the combined use in a lubricatingcomposition of organic oxygen bearing compounds and organic halogenbearing compounds.

I have discovered that certain oxygen-bearing organic compounds incombination with a mineral oilbase which also has added thereto certainorganic halogen bearing compounds'produce a lubricating compositionequal to and, in certain respects, superior to the result secured by theuse of a pure hydrocarbon oil as a lubricantor a composition includingin combination a pure hydrocarbon oil and certain addition agents suchas oranic halogen bearing compounds. The lubricating compositionaccording to my present invention is particularly applicable for use asan extreme pressure lubricant.

For a definition of extreme pressure lubrication and the distinctionthereof over low pressure or thick film'lubrication reference may be hadto the specification of my above mentioned copending application.

It is among the objects of my invention, therefore, to provide alubricating composition which shall be superior to any which hasheretofore been available. Other objects of my invention will appear asthe description proceeds.

To the accomplishment 'of the foregoing and related ends, saidinvention, then, consists of the features hereinafter fully described,and particularly pointed out in the claims, the following descriptionsetting forth in detail certain embodiments of the invention, thesebeing illustrative, however, of but a few of the various ways in whichthe principle of the invention may be employed.

Particularly stated, this invention comprises cured by the use of ahalogen alone.

bined use of both of such materials as addition agents to lubricatingcompositions which also contain a suitable lubricating oil such asmineral oil.

I have found that vvhile the addition of a halogen in the form of anorganic compound generally improves the lubricating properties of amineral oil, nevertheless, when such halogen is present in' the form ofcertain of the available halogenated organic compounds it is so stronglycombined that when used alone as an addition agent to a'mineral oil,theextreme pressure characteristics of the composition are not asimproved as may be desired for certain uses. The additional presence ofoxygen in such oxygen compositions, however, renders such. halogen moreactive so thatthe extreme pressure characteristics of the compositionare considerably better than that se- The oxygen referred to above maybe conveniently present in the composition in the form of oxygencontaining or bearing organic compounds.

Both the halogen bearing organic compounds and the oxygen bearingorganic compounds for purposes of convenience, may be classified asfollows:

I. Aliphatic, or carbon chain type A. Derivatives of hydrocarbons of theparaffin series, I Derivatives of hydrocarbons of the oleflne series (2)Hydrogenation products of naph-- thalene (e. g. decahydronaphthalenet,tetrahydronaphthaene e c. v (3) Naphthenes, naphthenic acid,

i et

(0) "0f mixed me such as derivatives of .in-

dene, hy ndene, hydranthra'cene, etc. 13. Hetero geneous ring'f typecompounds (a) 0 the aromatic or allied type including dc- I rivatives'ofpyridine, quinoline, etc.

(b) Other types such a farm and it's derivatiraes and derivatives oi.thiophene, pyrro e, e c.

The oxygen bearing derivatives of the foregoing compounds may also beclassified according to the nature of the attachment of the oxygen tothe molecule viz.:

I. Directly attached to one or more the case of:

(1) Ethel-s and analogous compounds (2) Compounds containing the =COHradicle, such as alcohols and other derivacarbon atoms, as in tives ofcarbinol (including phenols, cresols, naphthols etc.) (3.) Compoundscontaining the carbonyl (=C=) rndjcle, such as aldehydes, ketones,organic acids, esters and salts of organic acids, tide-acids and estersof thio-acids. (4) Compounds in which oxygen forms a part oi. the ringstructure, e. g. furan and its derivatives, anthraquinone, etc.

II. Indirectly attached through the means of some other atom, i. e., inthe form of an inorganic radicle, e. g.: Amide 0 xin1e ArsenatePerchlorate Arsenite Phosphate Chlorate Phosphite Chlorite SulphateCyanate flulphite Hydroxylamine Sulphinic acid Hypochlorite SulphoneNitrate Sulphonic acid Nitrite Sulphoxide Nitro Thio-phosphate NitrosoThio-sulphate Of the above enumerated compounds the can bo xylic acidsand the esters and salts of such acids are preferred, e. g., fatty oils,yegetable oils oleic acid, stearic acid, amyl acetate, butyl stearate,dibutyl phthalate, methyl salicylate, naphthenic acid, butylnaphthenate; sodium, calcium and aluminum stearates and oleates; sodium,calcium and lead naphthenates, aniline stearate, aniline oleate,stearanilid, quinoline oleate, quinoline stearate. p

The halogenated organic compounds emplo ed in accordance with thisinvention ar prefers. ly halogenated carbon ring compounds which arepreferably of the chlorinated species and par- '(b) Halogenated aminoderiva- .tives of diphenyl, e. g.

Chlorinated phenyl-anilines Chlorinated phenyl-toluidines (c)Halogenated hydrodiphenyls,

.e. g. I

Chlorinated phenyl hexahydrobenzene Chlorinated dodecahydrodiphenyl III.Naphthalene, such as:

ticularly the following compounds have been found to, produce verysatisfactory-results, viz.: Halogen bearing derivatives of:

I. Benzene, such as:

(1) Halogenated benzene, e. g.

(a) Monochlorbenzene' (b) The dichlorbenzenes, notablyDichlorhexahydrobenzene Y (dichlor cyclohexane) II. Diphenyl, diphenylbenzenes, such as:

(l) Chlorinated diphenyl (2) Halogenated derivatives of diphenyl,

such as.

(a) Halogenated homologs of diphenyl, e. g. Chlorinated phenyl-tolpanes(l) Chlorinated naphthalene (2) I-Ialogenated derivatives of naphthalenesuch as:

(a) Halogenated homologs naphthalenes, e. g.

Chlorinated'methyl naphthalene notably the alpha compound,

Chlorinated propyl, and I isopropyl substitution products of naphthalene(b) Halogenated amino -deriva- I tives of'naphthalene, e.- g.

Chlorinated naphthylamines (c) Halogenated hydronaphthalenes, e. g.

Chlorinated decahydronaphthalene IV. Phenanthrene and anthracene, suchas:

(1) Chlorinated phenanthrene, chlorinated anthracene (2) Halogenatedderivatives of phenanthrene and anthracene, such as' (a) Halogenatedhomologs, e. g.

Chlorinated 1 methyl phenanthrene Chlorinated 3 methyl phenanthreneChlorinated 9,10 methyl phenanthrene Chlorinated propyl and isopropylderivatives of phenanthrene such asretene Chlorinated a-methylanthracene Chlorinated B-methyl anthracene Chlorinated dimethylanthracenes Chlorinated propyl and isopropyl substitution products ofanthracene (b). Halogenated amino derivatives, e. g.

Chlorinated phenanthrylamines Chlorinated anthramines (c) Halogenatedhydrophenanthrenes and halogenated v hydranthracenes V. Chrysene, andpicene.

n will be noted that the above enumerated examples or carbon ringcompounds which are preferably employed are compounds or the aryl typ i.e compounds containing benzenoid ring. structures and are also of thetype in which the halogen is directly attached to an atom which is apart of such ring structure.

Compounds of types related to certain of the above are also particularlyusefulsuch as halogen bearing derivatives of pyridine quinoline,pyrrole, thiophene and furan. c

As a matter of convenience, the halogenated diphenyls and substituteddiphenyls, as well' as halogenated substituted benzenes where two ormore phenyl groups are directly linked may be inclusively referred to ashalogenated polyphenyls.

The base of the lubricating composition may be, as previously indicated,any oily material, preferably mineral 'oil; however, other material suchas fixed oils, and special oils such as sulphurtreated oils, may beadvantageously employed for particular purposes. The optimum amount ofthe addition agents to be employed in conjunction with the oil base asabove defined, will depend upon the particular character of suchcompounds, i. e., their physical characteristics and especially theireffect .upon the viscosity of the oil to which the same are added. Theparticular use for which the lubricant is intended is also a governingfactor in determining the amount of the compound or compounds to beadded.

My invention, as above explained, contemplates the addition to asuitable oil base of minor amounts of addition agents in suchproportionsas not to materially reduce the viscosity of the oil. Since the loss ofsuch addition agents by volatilization will in general be less forhigher boiling material, the boiling point of the addition agents shouldbe at least 125 C. and preferably above 140 C.

Itis to be understood. that the so-called addition agents referred toherein shall be sub.

stantially oil-soluble or of such nature that they may be included inthe composition in the form of a stable colloidal suspension. It shouldalso be noted that certain of the addition agents contemplated by thisinvention, while soluble inoil do not dissolve readily therein. Whensuch compounds are used they may be first dissolved in materials suchas, benzene, the chlorbenzenes, the higher alcohols'such as amylalcohol, acetone, petroleum naphtha, carbon tetrachloride,tetrachlorethylene, aniline, tricresyl phosphate,

- etc., and the resulting solution then added to the lubricatingcomposition.

In the case of organic oxygen compounds which are very strongly adsorbedby metal surfaces (e. g., fatty acids and derivatives of them) if toomuch is added, the halogen compound may be prevented from functioning toincrease the film strength, probably by being displaced from such Iployed, such as hexachlorethane, acetylene tetra surfaces. It is,therefore, advisable to determine the amount of the oxygen compound usedwhich will have the optimum efiect.

In general, the lubricating composition, in accordance with myinvention, may compris th so-called addition agents in their pure stator with a minor amount of mineral oil added thereto; however, formost'uses, a composition comprising a major proportion of a suitable oilbase and a minor proportion of the addition agents will be found mostsatisfactory.

An example of a composition comprising such addition agents in theirpure state without the addition of a mineral oil would be a mixture ofchlorinated diphenyl and an ester of stearic acid, for example, butylstearate. In this case on account of the high viscosity of the organichalo-,

gen compound, nomineral oil is required for "thick-film lubrication, andthe improved results due to the presence of oxygen may be obtained bythe sole. addition of such organic oxygen compounds, usually in minoramounts.

A-s'above pointed out, the halogenated organic ring compounds arepreferred over the halogenated open chain compounds as the source forthe halogen or more'specifi'cally, the chlorine. The reason for suchpreference i that chlorine is sufficiently stable in the ring compoundsso.-

that in the presence of water there will be.no appreciable amount ofhydrolysis which would result in corrosion of the metal parts with whichthe composition comes in contact. In the form of the ring compounds, thechlorine is sufllciently closely combined so that it will becomeavailable to chemically react with the bearing surfaces to produce thedesired results only under the conditions imposed by the relativemovement between such surfaces. In certain of the ring compounds,however, the chlorine is so-closely attached that it is not madesufiiciently available for the desired results, even under theconditions imposed by the relative movement between the bearings. Theadditional presence of oxygen, however, cures this difficulty and it isthis reason, among others, which may explain the unusual and unexpectedresults secured by the combined use in the composition of the oxygen andchlorine.

, This invention also contemplates the use in lubricating compositionsof halogenated carbon chain'compounds and a separate organic oxy-. genbearing compound for the purpose of increasing the film strengthfi Suchcompositions are especially useful where unusuallyextreme conditions ofpressure exist, the activity of the halogen being further increased, asin the case of the ring compounds, by the addition of organic oxygencompounds thus increasing the range of usefulness of such compositions.

Of the chain compounds which may be em- For the purpose of lubricatingand reducing the friction between the relatively moving parts of aninternal combustion engine, such as crank case bearings, piston andcylinder surfaces, as well as piston rings and valves, the compositionwill preferably comprise a major proportion of an oil base such .asmineral oil and concentrations of from of 1% to 2% of the additionagents. If the valve structure of such engine is to be lubricatedseparately from the remainder of the engine or by means connecting in anauxiliary fashion, the lubricating compositionwillpreferably contain alarger amount of such addition agents, i. e., from about 2 to 10%.

The lubricating compositions referred to herein have a particularadvantage in the tendency of the compounded lubricantemployed to keepdown carbon formation and hence, such compositions are particularlyapplicable for the lubrication of the upper parts, i. e., pistons,valves. piston rings, etc. of an internal combustion engine bydissolving the specified composition in" ency. for bearing surfaces solubricated to become scored or to seize at higher pressures than areallowable with ordinary lubricants.

Second.-The friction between the bearing surfaces is reduced, especiallyin the higher Serial Number Other modes of applying theprinciple of myinvention may be employed instead of the one explained, change beingmade as regards the materials employed in carrying out the process,

provided the ingredient or ingredients stated in any of the followingclaims or the equivalent of such stated ingredient or ingredients beemployed.

I therefore particularly point out and distinctly claim as my invention:

1. A lubricant compound of high film strength and lower coefficient offriction, over a significant range of working conditions, than any oneof its constituents or any two of its constituents combined, comprisinga major proportion of mineral lubricating oil, a minor proportion of asubstantiallyi neutral, body of oil-film strengthening, oil-soluble,aromatic hydrocarbon having chlorine in chemical combination therewithof the type illustrated by chlor-naphthalene and chlor-diphenyl, said.body substantially nonvolatile at ordinary temperatures, and a minorproportion of another bodyof friction-reducing, oil-soluble organiccompound having oxygen in saponifiable chemical combination therewith,

the total proportion of said bodies being within the limit of theircombined solubility in said I ricating oil. k

2. A lubricating composition containing, as a principal lubricatingconstituent a major amount of minerallubricating oil with the propertiesof compounds being of the type which will notsubstantially evaporatefrom such lubricating com position .at ordinary temperatures, and saidlubricant characterized by a higher film strength or lower coefficientof friction respectively, over carbon ring compoundand an oil-solubleorganic oxygen compound, the total proportion of said compounds 'beingwithin their combined solu-' bility in said mineral lubricating oil andsaid compounds being of the type which will not substantially evaporatefrom such lubricating composition at ordinary temperatures, and saidlubricant characterized by a higher film strength or lower coefficientof friction respectively, over a' significant range of workingconditions, than similar lubricant compounds from which said halogen andoxygen compounds respectively have been omitted.

4. A lubricating composition containing as aprincipal lubricatingconstituent a major amount of mineral lubricatin oil with the propertiesof such composition affecting its use as a lubricant improved byincorporating therein an effective minor amount of both an oil-solublehalogenated organic compound and an oil-soluble organic oxygen compound,the total proportion of said compounds being within their combinedsolubility in said mineral lubricating oil and said compounds being ofthe type having a vapor pressure less than atmospheric at a temperatureof 140 C., and said lubricant characterized by a higher film strength orlower coefficient of friction respectively, over a significant range ofworking conditions, than similar lubricant compounds from 5. Alubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such' composition affecting its use as a lubricantimproved by incorporating therein an effective minor amount of both anoil-soluble halogenated organic compound and an oil-soluble ether, thetotal proportion of said compounds being within their combinedsolubility in said mineral lubricating oil and said compounds being ofthe type which will not substantially evaporate from such lubricatingcomposition at ordinary temperatures, and said lubricant characterizedby a higher film strength or lower coefiicient of friction respectively,over a significant range of working conditions, than similar lubricantcompounds from been omitted.

' 6. A lubricating composition containing as a which said halogen andoxygen respectively have principal lubricating constituent a majoramount of mineral lubricating oil with the properties of such.composition affecting its use as a lubricant improved by incorporatingtherein an effective minor amount of both an oil-soluble halogenatedorganic compound and an oil-soluble organic carbonyl compound, the totalproportion of said'compounds being within their. combined solubility insaid mineral lubricating oil and said compounds a significant range ofworking conditions-than similar lubricant compounds from which saidhalogen and oxygen compounds respectively have been'omitted.

3. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein an effective minor amount of both anoil-soluble halogenated being of the type which will not substantially}evaporate from such lubricating composition at ordinary temperatures,and said lubricant char acterized 'by' a higher film strength or lowercoeflicient of friction respectively, over a significant range ofworking conditions, than similar lubricant compounds from which saidhalogen com-1' pound and said oxygen compound respectively have beenomitted.

'7. A lubricating compositioncontaining as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting itsuse as a lubricant improvedby incorporating therein an-eifective minor amount of both anoil-soluble halogenated organic compound and an oil-soluble ester, the

total proportion of said compounds being within their combinedsolubility in said mineral lubricating oil and said compounds being ofthe type which will not substantially evaporate from such lubricatingcomposition at ordinary temperatures, and said lubricant characterizedby a higher film strength or lower coeificient of friction respectively,over a significant range of working conditions, than similar lubricantcompounds from which said halogen and oxygen compounds respectively havebeen omitted.

8. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricantimproved' by incorporating therein an effective minor amount of both anoil-soluble'halogenated organic compound and an oil-soluble ketone, thetotal proportion of said compounds being within their combinedsolubility in said mineral lubricating oil and said compounds being ofthe type which will not substantially evaporate from such lubricatingcomposition at ordinary temperatures, and said lubricant characterizedby a higher film strength or lower coeflicient of friction respectively,over a significant range of working conditions, than similar lubricantcompounds from which said halogen and oxygen compounds respectively havebeen omitted.

9. A lubricating composition consisting entirely of the combination ofan oil-soluble halogenated organic compound and an oil-soluble organicoxygen compound, the proportion of said compounds being within theirmutual solubility and said compounds being of the type having a vaporpressure less than atmospheric of a temperature of 140 C., and saidlubricant characterized by a higher film strength or lower coefficientof friction respectively, over a significant range of workingconditions, than said halogen and oxygen compounds, respectively, whenused alone.

10. A lubricant composition'comprising a solution of an oil-solublehalogenated organic compound and an oil-soluble organic oxygen compound,said compounds bein present within the limit of their mutual solubilityand of the type having a vapor pressure less than atmospheric at atemperature of 140 C., said composition being effective to provide alubricant having a higher film strength or lower coeffieient of frictionrespectively over a significant range of working conditions, thansimilar lubricants from which said halogen compound and said oxygencom-.

15. A composition in accordance with claim 2 in which the halogenatedorganic compound is chlorinated decahydronaphthalene.

CARL F. PRUTTON.

